The product thereof



Reissued r. 2, 1935 PROCESS OF TREATING GASOLINE AND' THE PRODUCT THEREOF August P. Bjerregaard, Dayton, Tenn, assigncr, by mesne assignments, to Gasoline Antioxidant Company, Wilmington, Del.,

Delaware a corporation of N0 Drawing. Original No. 1,761,810, dated June 3, 1930, Serial No. 126,090, for reissue May plication 609,548

26 Claims.

This invention relates to a process for the treatment of gasolines for the purpose of rendering them resistant to the action of light and particularly to the action of sunlight.

Y It is well known that most gasolines, especially .those gasolines which are blends of cracked gasoline and the so-called straight run gasoline derived directly from natural crude petroleum oils by distillation, lose their clearness when exposed to sunlight and even when exposed to diffused daylight. This loss of clearness is due to a cloudy formation or precipitate which develops in the gasoline because of its exposure, which cloudy formation later separates out as a gummy resinous-like material. Frequently the gasoline becomes discolored due to the action of light, while in other cases the cloudy formation is milkish white.

The result of the action of light on gasoline as above referred to is very detrimental because the cloudiness or discolor" detracts from the appearance of the gasoline and more particularly because the gummy resinous material settles out and adheres to the glass sides of measuring cylinders or bowls discoloring them and rendering them unsightly. Furthermore, when the gasoline containing this cloudy formation or resinous material is used as a motorfuel the gummy resinous material has a tendency to deposit in the feed lines, on the parts of the carbureter and other parts of the engine with which it comes into contact and thereby interferes with the proper functioning of the motor.

The object of the present invention is to provide a process for the treatment of gasolines which are subject to the defect or defects referred to above'whereby. the formation of cloudiness or discoloration therein is prevented when the gasoline is exposed to light.

In accordance with the object stated the invention comprises forming a permanent mixture by adding to the gasoline to be treated a substance which will render the gasoline stable in the presence of light, that-is, a substance which will prevent the appearance or formation of the cloudiness or discoloration referred to. p

The process of the present invention difiers from known processes of treating gasoline in that no residue .or polymerized hydrocarbon material is removed by filtering or. decanting as is the case where the gasoline is treated with an acid, an alkali or a solution of some salt.

I have found by extensive investigation in respect to thisphenomenon of cloud formation in gasolines exposed to light, that all substances July so, 1920. An- 5, 19s2, swarm.

(Cl. 4H)

soluble in' gasoline may be divided into three classes, first'thosein which accelerate the formation of cloud, second, those which retard or prevent the formation of cloud, and third, those which neither accelerate or inhibit and which are, so to speak, indiflerent to the phenomenon of cloud formation in gasolines exposed to light.

My novelprocess, therefore, is based on the fact discovered by me, that some substances when mixed with gasoline possess the above mentioned retarding or inhibiting influence on cloud formation when the gasoline mixture is exposed to light. These retarding or cloud preventing substances act efliciently when present in extremely small quantities, suggesting that their effect is due to acatalytic influence, or assuming that light acts as a catalyst in causing the formation of cloud in gasolines, the influence referred to may be more properly called anti-catalytic in its nature since it annuls the action of light.

In carrying the process into effect a small quantity of one or more of these substances which retard or prevent the formation of cloud in gasoline when exposed to light is mixed. with or dissolved in the gasoline in any convenient'manner either before or after the gasoline leaves the refinery.

Among the substances foimd to be suitable anti-catalysts in the process are:. certain complex hydrocarbons, for example, anthracene, phenathrene and certain .phenolic substances, for example, phenol, orthcresol, metacresol, paracresol and guaiacol (a dihydroxy benzene derivative or catechol known as 'methylcatechol). These substances all contain one or more benzene rings and therefore may be referred to as derivatives or. homologues of benzene. While I have named several substances possessing this anti-catalytic property I have found anthracene to have this property to a much greater extent than the others. a r

It is also true that the type or character of the gasolinetreated has some effect on the usefulness of any particular cloud retarding substance.

For example it may be necessary with a gasoline from a certain source, to use larger amounts of the particular retarding substance and in some cases to use a different substance since it is obvious that all substances which may be used do not act with equal efficiency. The extensive use of anthracene as an anti-catalyst has shown that gasolines from certain sources and from certain refining treatments require less anti-catalyst than other gasolines. The amount of anti-catalyst used as intimated above depends on the gasoline and the retarding substance, but I have found that two to four pounds of the anti-catalyst to 100 barrels of gasoline (approximately 0.008% to 0.016% anti-catalyst, on the basis of 66 B. gravity gasoline) is sufiicient in most cases. In using anthracene alone from 2 to 15 pounds per 1000 barrels of gasoline have been found to be sufficient in most cases. v

' No special apparatus is required for the process, it being sufiicient to dissolve the anti-catalyst in the gasoline. If necessary the mixture may be agitated to facilitate solution of the substance in the gasoline and this agitation may be accomplished by any known method or apparatus.

The presence of the anti-catalyst in the treated 3 gasoline in no way detracts from the usefulness "of the gasoline as' a motor fuel since the subregular refinery treatment with sodium plumbite but the anthracene or other compound is preferably added after the gasoline has been sweetened by the plumbite treatment.

The treatment of gasoline by the present invention is intended primarily to make gasoline light stable and prevent the formation of resinous compounds in them. This process may be.

applied to any gasoline, which has been refined and has a proper color, whether or not the refining has employed the use of well known chemicals or filtering for getting the propercolor. In other words, the present invention may be applied to-any gasoline as supplemental to the-usual refiningand treating processes, in order to make the gasoline light stable and prevent the formation of resinous compounds.

The following examples will illustrate the effect of sunlight on the various types of gasoline and the gum or cloud retarding or accelerating effect of the substances added.

Example No. 1.In the following tests the gasoline used was a -50 blend of straight-run and cracked gasoline derived from Kansas crude,

each portion of the blend being separately sweetened to the doctor test by doctor solution and a trace of sulphur.

Sample No. 1.-Nothing added.

Sample No. 2.2 milligrams of anthracene added per 110 c. c. of gasoline.

Sample No. 3.4 milligrams of anthracene added per 110 c. c. of gasoline.

Sample No.v 4. -6 milligrams of anthracene added per 110 c. c. of gasoline.

Each of these samples was exposed to sunlight for nine hours after which they showed the following condition: a

Sample No. 1.Dense, cloudy and yellow.

Sample No. 2.-Cloudy and yellow Samples 3 and 4.-Clear, brilliant and white with no discoloration.

Example No. 2.-With straight-run gasoline derived from Kansas crude and sweetened by "doctor treatment the following results were obtained: a

Sample No. 10.Nothing added.

- Sample No. IL-2 milligrams of anthracene added per 110 c. c. of gasoline.

Sample No. 12.4 milligrams of anthracene added per 110 c. c. of gasoline.

After exposing these samples to sunlight for four hours the following condition were shown:

Sample No. 10.Very cloudy and slightly yellowish.

Sample No. 11.-Extremely faint haze but whiten Sample No. l2.Clear and white.

Example No. 3.'I'he gasoline used in the following tests was a-50-50 blend of straight-run and cracked gasoline derived from a Healdton (Texas) crude, each sample being made sweet to the "doctor test.

Sample No. 14.Nothing added.

Sample No. 15.6 milligrams of anthracene added per 110 c. c. of gasoline.

Sample No. 17.--10 milligrams of carbazol A added per 110 c. c. of blend.

Sample No. 18.10 milligrams of carbazol B added per 110 c. c. of blend.

After two hours exposure. to sunlight these samples showed the following conditions:

- Sample No. 14.-Cloudy.

Sample No. 15.Clear.

Sample No. 17.Very cloudy; more cloudy than No. 14.

Sample No. 18.-Very cloudy; more cloudy than No. 14.

The examples and tests given above clearly show the cloud or gum retarding effect of anthracene which is similar to other substances mentioned. Likewise the results illustrated by Samples No. 17 and No. 18 show the effect of accelerating agents on gum formation.

As a result of the action of an anti-catalyst such as anthracene in preventing gum formation in cracked gasoline or motor fuels containing unsaturated or other unstable compounds, the olefins or other unsaturated substances which are ordinarily polymerized to gains, are preserved in substantially their original forms in the motor fuel or gasoline. The anti-catalyst, therefore, besides preventing gum formation has the additional effects of preventing loss of important gasoline constituents, and of increasing the antiknock value of the gasoline.

Where in the claims anthracene or any of the other substances mentioned above are specified,

it is to be understood that the claims are intended to cover the use of equivalent substances render them light stable, comprising agitating V gasoline in the presence of sodium plumbite to render the gasoline sweet, and dissolving in the gasoline a small proportion of anthracene;

2. The process of inhibiting gum formation in a'blend of cracked and straight run gasoline,

which comprises mixing and dissolving in said, gasoline anthracene, said anthracene being used in a ratio of not more-than four pounds of an- .thracene to 100 barrels of gasoline.

"comprises refining the gasoline with sodium plumbite, and thereatfer dissolving in the gasoline a small proportion of a substance adapted to make the refined gasoline stable to light, said substance comprising substantially only anthracene.

5. The process of inhibiting the formation of gum in cracked gasoline, which comprises mixing therewith and dissolving therein material selected from the aromatic group consisting of anthracene, phenanthrene and hydroxy benzene compounds, said material being mixed with the gasoline in suflicient quantity to inhibit the formation of gum therein but'in a ratio of not more than about one one-hundredth of one per cent by weight of the gasoline.

6. The process of inhibiting the formation of gummy precipitates in a motor fuel comprising a blend of cracked'and straight run gasoline, which comprises mixing therewith and dissolving therein a substance selected from the group consisting of anthracene, phenanthrene and bydroxy benzene compounds, whereby said fuel is stabilized to prevent the precipitation of gum therein, said substance being used in a ratio of not more than two pounds to 100 barrels of gasoline treated. i I

'7. The process of inhibiting gum formation in gasolines containing gasoline produced from the cracking of mineral oils, which comprises mixing therewith and dissolving therein an aromatic benzene homologue acting as an anti-catalyst and selected from a group consisting of anthracene, phenanthrene, phenol, ortho-cresol, metacresol and para-cresol, said homologue being used in a ratio of not more than about 0.016

I per cent by weight of the gasoline treated.

8. A motor fuel mixture, comprising cracked gasoline and added anthracene dissolved therecene and in not more than about one one-hundredth of one percent by weight of the mixture.

10. A motor fuel mixture, comprising cracked gasoline, and from two to four pounds of an added organic anti-catalyst to one hundred barrels of motor fuel, said anti-catalyst comprising substantially only anthracene.

11. A motor fuel mixture, comprising cracked gasoline,- and approximately one one-hundredth of one per cent by weight of an added organic anti-catalyst selected from the group consisting of anthracene, phen'anthrene and hydroxy benzene compounds dissolved in gasoline.

12. A gum and cloud-free motor fuel comprising cracked gasoline and an added aromatic benzene homologue acting as an anti-catalyst selected from a group consisting of anthracene,

bon motor fuel distillate of less-readily. detonat-- ing type normally tending to develop gum-forming constituents containing an added hydroxy benzene compound in quantity suflicient to prevent development of such gum-forming constituents.

14. A method of stabilizing the characteristics stituents.

.of a monohydroxy benzene derivative suflicient to substantially inhibit gum-formation in said distillate.

15. A cracked unsaturated hydrocarbon motor fuel distillate normally tending to develop.

gum -forming constituents containing an added hydroxy aromatic compound in quantity sufiicient to prevent development of such gum-form ing constituents.

16. A cracked unsaturated hydrocarbon motor fuel distillatenormally tending to. develop gum-forming constituents containing an added phenolic compound in quantity sufficient to prevent development of such gum-forming concompound inquantity sufficient to prevent development of such gum-forming constituents.

18. A motor fuel miirture comprising cracked gasoline normally tending to develop gum-forming constituents containing an added derivative of a monohydroxy aromatic compound in quantity sufficient to prevent development of such gum-forming constituents.

19.- The method of stabilizing the character istics of a cracked unsaturated hydrocarbon motor fuel of the less readily detonating type normally tending to deteriorate and develop gumforming constituents, which comprises adding thereto prior to such deterioration a small proportion of a cresol sufficient to substantially inhibit gum formation in said distillate.

20. A motor fuel mixture comprising cracked gasoline normally tending to develop gum-forming constituents and a small proportion of an added cresol in quantity suflicient to prevent development of such gum-forming constituents.

- 21. A motor fuel, comprising cracked gasoline of the less-readily detonating type normally tending to deteriorate and develop gum-forming constituents on storage and containing added anthracene in quantity suflicient to prevent the development of such gum-forming constituents.

22. A motorfuel, comprising cracked gasoline of the less-readily detonating type normally tending to'deteriorate and develop gum-forming constituents on storage and containing an added aromatic benzene homologue selected from a group consisting of anthracene, phenanthrene,

phenol, ortho-cresol, meta-cresol, and paracresol, said homologue being present in quantity sufllcient to prevent the development of such gum-forming constituents. I

23.1 The method of stabilizing the'characteristics of cracked gasoline of the less-readily detonating type normally tending to deteriorate and develop gum-forming constituents, which comprises adding thereto prior to such deterioration a small proportion 'of a derivative of a compound comprising a hydroxylated benzene nucleus in quantity sufficient to prevent development of such gun-forming constituents,

24. A motor fuel, comprising cracked gasoline of the less-readily detonating type, normally tending to deteriorate 'and develop gum-forming constituents on storage and containing an added compound comprising a mono-hydroxylated benzene nucleus in quantity suflicient to prevent the 26. A motor fuel comprising cracked gasoline development of such gum-forming constituents.

25. The method of stabilizing the characteris tics of a cracked unsaturated motor fuel of the less-readily detcnating type, normally tending to deteriorate'and form gum-forming constituents, which comprises adding thereto prior to such deterioration a small proportion of a compound ,comprising a hydroxylated benzene nucleus in quantity suflicient to prevent development of such gum-forming constituents.

of the less readily detonating type normally tending to deteriorate and develop'gum-forming constituents and containing an added aromatic compound selected from the group consisting of anthracene, phenanthrene and hydroxy benzene compounds, .said compound being present in quantity sumcient to prevent the development 01' such gum-forming constituents.

AUGUST P. BIERREGAARD. 

